Artificial Photosynthesis Technology for

Solving Environmental and Energy Issues

 Yoshihiko Imanaka  Toshio Manabe  Toshihisa Anazawa  Hideyuki Amada

To create a sustainable society that is friendly to the global environment for the future, de-
creasing the amount of greenhouse gases such as CO2 is an urgent matter, and also producing
storable clean energy that does not depend on fossil fuels is demanded. Artificial photosyn-
thesis consisting of a light reaction dependent on a light source and dark reaction not related
to it is technology with which oxygen, hydrogen, and organic products are produced artificially
by using solar energy, water, and CO2. Recently, this has come to be regarded as an important
technology for solving both the environmental and energy issues we face, as described above.
Fujitsu has researched this technology as one of the important basic technologies relating to
energy and the environment in order to achieve a sustainable human-centric society for the fu-
ture. This paper introduces basic research regarding materials and devices applied to the light
reaction and dark reaction that we are currently investigating in order to develop a highly effi-
cient artificial photosynthesis system producing storable energy by using CO2, water molecules,
and electrons generated from a photocatalyst irradiated with solar light.

1. Introduction that performs better than the photosynthesis of plants

The issues relating to global warming, natural
resource depletion, and radioactive contamination
caused by nuclear power plant accidents demand the
development of next-generation technology that can
produce storable clean energy, while decreasing the
emissions of greenhouse gases such as CO2, for a fu-
ture sustainable society. There are expectations that a
hydrogen society and methanol society using hydrogen
and methanol as an energy source, respectively, can be
feasible examples. Producing storable clean energy
sources with a small environmental load is important
for building a green smart city utilizing information and
communications technology (ICT), and it can be useful
in a situation where social infrastructure fails to func-
tion due to a natural disaster such as an earthquake.
It is well known that plants produce organic prod-
ucts such as starch from solar light, water, and carbon
dioxide, store the products and consume them for
growing, in the natural world. The photosynthesis of
plants is the ideal energy creation technology which
meets all of the requirements relating to our current so-
cial issues. Therefore, creating artificial photosynthesis
would solve our environmental and energy problems.
This paper introduces the basic concept and
fundamental material research regarding artificial
photosynthesis technology that Fujitsu is working on as
environmental and energy R&D.
2. Artificial photosynthesis technology
Technology that produces storable energy sources
such as hydrogen, methanol, and methane by irradi-
ating solar light on a photocatalyst is called artificial
photosynthesis, and there are high expectations that
it will be remarkable environmental and energy tech-
nology.1) An artificial photosynthesis reaction system
is shown in Figure 1. An anode coated with a photo-
catalyst and a cathode for producing organic reaction
products are installed in water containing CO2 gas. By
irradiating solar light on a photocatalyst formed on the
anode, the light energy is converted to high-energy
electrons and simultaneously a hole with high oxida-
tion capability is formed.
When light energy more than the band gap be-
tween the conduction band composed of electrons in

44 FUJITSU Sci. Tech. J., Vol. 53, No. 2, pp. 44–50 (February 2017)
 Y. Imanaka et al.: Artifi cial Photosynthesis Technology for Solving Environmental and Energy Issues

e–
Light Reaction (electron) Dark Reaction

Anode Cathode

Conduction Catalyst metal

H2O e– band

Conducting substrate
Visible light
Conducting substrate

H2/H2O H2O responsive light

CO2
(hole) photocatalyst
h+
H2O/O2 (water)

O2 Valence Solar light H+ CO2 adsorption material

band H2 (metal organic framework)
(proton)
(hydrogen)

O2
(oxygen)

CO2 multi-electron reduction

HCOOH
2e–, 2H+ 2e–, 2H+
CO2 HCHO CH3OH CH4
–H2O
(formic acid) 2e–, 2H+ 2e–, 2H+
CO –H2O
(carbon dioxide) 2e–, 2H+ 2e–, 2H+ (formaldehyde) (methanol) (methane)
–H2O
(carbon monoxide)

Figure 1
Concept of artificial photosynthesis.

the outermost electron shell, and the valence band next section describes research regarding the light re-
composed of highest energy orbitals in which all elec- action and the dark reaction, in detail.
trons are occupied is supplied, the electrons in the
valence band are excited to a conduction band, and a 3. Development of light reaction
hole is formed in the valence band. The formed hole Figure 2 shows the wavelength distribution of
reacts with water, and then oxygen is formed on the solar light spectrum. It consists of light with continu-
anode. The electrons formed by light energy are trans- ously different wavelengths. Since TiO2, which is widely
mitted to the cathode through conductive wiring. By used as a photocatalyst, has a wide band gap, higher
reacting protons (H+), electrons, and carbon dioxide on energy light with a short wavelength (e.g., ultra-violet
the cathode, organic products such as hydrogen, metha- light) is needed for exciting electrons. Therefore, only
nol, and methane are synthesized. In order to generate about 5% of all solar light energy power is used.2) A
oxygen on the anode, the hole energy potential in photocatalyst with a shorter bandgap is required in a
the photocatalyst material should be higher than the light reaction so that longer solar light wavelengths
oxidation-reduction potential of water. And to syn- can be used. In addition, to provide holes and electrons
thesize hydrogen, methanol, and methane, electrons needed for the reaction in artificial photosynthesis, the
having a higher reduction potential than the oxidation- oxidation-reduction potential of water and hydrogen
reduction potential of carbon dioxide should be sup- or carbon dioxide should be located between the va-
plied. Artificial photosynthesis is technology that lence band maximum (VBM) and the conduction band
combines a light-dependent reaction on an anode with minimum (CBM). However, no materials that satisfy
a dark reaction, which is not related to solar light. The the two above requirements exist, generally. For this

FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017) 45

Y. Imanaka et al.: Artifi cial Photosynthesis Technology for Solving Environmental and Energy Issues

reason, there has recently been active R&D on materi-
als that can contribute to photosynthesis in the range
of visible light.3)
To increase the reaction efficiency in a light
reaction, it is imperative to use a photocatalyst that
satisfies the requirements described above for the
anode. Besides that, producing a nanoparticulated
structure with a large surface area is required to
promote the reaction with solar light and water. In ad-
dition, to transport the electrons excited by solar light,
it is necessary to form a film and interface structure
indicating excellent electron conductivity on an elec-
trode substrate. However, meeting these demands
simultaneously is difficult using conventional methods.
Energy (eV)
2 4 3.5 3 2.5 2 1.5
Ultraviolet Visible light
Spectral irradiance (W/m2/nm)
Fujitsu succeed in forming a nanoparticulated struc-
ture consisting of a narrow-band-gap photocatalyst
and strongly adhered it to a conducting substrate by
making use of original technology called nanoparticle
deposition (NPD)4) originally developed as a deposi-
tion method for electronic ceramics in microelectronics
packaging. The particles consisting of a visible-light
response photocatalyst—a GaN-ZnO solid solution—and
gas are mixed, and then the nanoparticles that are
strained and pulverized during the deposition process
are sprayed on a substrate using a nozzle. Finally, a
nanoparticulated photocatalyst film can be formed on
a conducting substrate (Figure 3).
Figure 4 shows a cross-sectional view of a photo-
catalyst film formed on a conducting anode substrate
observed with a transmission electron microscope. In
this figure, a lamellar structure indicating accumulated
1 100 nanoparticles can be observed. Around the top of the
Infrared
Fraction of total irradiance (%)

80
1.5
Energy (eV) 60
1 =
1,240 NPD film
Wavelength (nm)
40
Conducting substrate

0.5
20

0 0
300 500 700 900 1,100 1,300
Wavelength (nm)

Figure 2
Wavelength distribution of solar light spectrum.

Raw material
particles
Oriented NPD film

Conducting
substrate

Nozzle

Ga/Zn particle
Crushed
N/O particle
plate-like
particulates TEM photograph: Ikuhara lab., the University of Tokyo

Figure 4
Figure 3 Atomic structure of photocatalyst film with a transmission
Concept of deposition of photocatalyst film by NPD. electron microscope (TEM) observation.

46 FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017)


film, a fluctuation in atomic distance in crystals due
to atomic misalignment can be observed. We clari-
fied that electron orbitals are expanded and the band
gap of the photocatalyst film can be reduced finally by
introducing a strain in crystals and forming disordered
atomic arrangements in the NPD process (the detailed
mechanism will be described later).
In the example of Figure 5, the bandgap of 2.53
eV of the raw material is successfully lowered to a band
gap of less than 2.0 eV by applying the NPD process.
As a result, we found that the covering wavelength re-
gion can be expanded by more than 25% by using a
modified GaN-ZnO film with our NPD process.5)
To clarify the phenomenon of how the band gap,
which is inherent to material primary, is reduced after
the NPD process, the characteristics of the NPD film and
raw powder were analyzed in detail using X-ray diffrac-
tion (XRD), X-ray absorption fine structure (XAFS) and
hard-X-ray photoelectron spectroscopy (HAXPES) in the
SPring-8 synchrotron radiation facility, Hyogo, Japan.
From these analysis results, we found that no difference
was detected between the NPD film and raw powder in
terms of crystal structure, but the atomic distance be-
tween metals (Ga and Zn) in crystals deviated in the
NPD film. In contrast, it was found that the atomic
distance between metal (Ga and Zn) and non-metal (N
and O) in crystals was not changed, comparing the NPD
film and raw powder.
To investigate the correlation between the
Material: GaN-ZnO solid solution
Photocatalyst film
produced by NPD
(band gap: 1.97 eV)
Absorbance (a.u.)
Raw material
(band gap: 2.53 eV)
300 400 500
Wavelength (nm)
Figure 5
Reflection/absorption properties of photocatalyst film
developed for light reaction.
FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017)
Y. Imanaka et al.: Artificial Photosynthesis Technology for Solving Environmental and Energy Issues
deviation of atomic position in the crystal structure and
decrement of band gap, a simulation was carried out
with a first-principles calculation using density func-
tional theory (DFT) applying pseudopotential.
GaN-ZnO has a hexagonal wurtzite structure, and
metal atoms are bonded to non-metal atoms alter-
nately. The metal atoms are located in the center of
a tetrahedron consisting of four apexes of non-metal
atoms. Ga or Zn in the metal sites and N or O in the
non-metal sites are randomly occupied respectively
[Figure 6 (a)].6) Every atom is bonded in a zigzag
manner in a crystal structure, as shown in Figure 6 (b).
The angles between the center atom of the tetrahedron
and the atoms of the apex are about 110 degrees in raw
material. In a film, as shown in Figure 6 (c) although
the distance between directly bonded metal atoms
and non-metal atoms is kept constant, the distance
between metal atoms deviates. In the model where
the distance between metal atoms deviates while there
is a constant distance between metal atoms and non-
metal atoms, it is found from a simulation that the
bandwidths are expanded and band gap is narrower.
Figure 6 (d) shows an example of the density of state
(DOS) separated in every orbital forming GaN-ZnO.
In a metal oxide and a metal nitride, a valence
band and a conduction band is formed by a metal-
oxygen bond and metal-nitrogen bond, and as a result,
a band gap is generated. It is considered that in the
film deposited by NPD, the partial mutual interaction
between metal atoms caused by the deviation of metal
atom distance results in expanding the bandwidth of
the valence band and conduction band, and the band
gap of an NPD film is narrower [Figure 6 (e)].7)
4. Development of dark reaction
In the dark reaction, organic products such as
methanol and methane are generated on a cathode by
making use of the electrons produced by a light reac-
tion and protons. When a proton is directly reduced,
hydrogen is generated. When carbon dioxide is sup-
plied and a higher-level reduction reaction occurs,
like the photosynthesis of a plant, storable organic
600 700
products can be generated. In the latter case, carbon
dioxide is reduced by the reaction of two electrons and
two protons to an organic product. The reduction pro-
ceeds in succession from carbon dioxide to formic acid
or carbon monoxide, formaldehyde, methanol, and
47
Y. Imanaka et al.: Artificial Photosynthesis Technology for Solving Environmental and Energy Issues

O O

N
N

O
O

Cross
N N
section “s”

(b) Atomic arrangement (c) Atomic arrangement

of cross-section “s” of cross-section “s”
(a) Structure of GaN-ZnO without fluctuation with fluctuation

Ga8Zn8N8O8

O 2p
Density of states (a.u.)

N 2p

Zn 4s Ga 4p
Band gap
Ga 4s Band
gap Without fluctuation
Zn 4p
With fluctuation

–8 –6 –4 –2 0 2 4 6 Conduction band Valence band Energy

Energy (eV)
(d) Density of states (e) Schematic diagram for band gap lowering

Figure 6
DFT simulation.

methane (Figure 1). We researched the cathode mate-
rial for use in a dark reaction for effectively carrying out
multi-electron reduction. Conventionally, preferentially
forming organic products except formic acid and carbon
monoxide has been difficult in terms of carbon dioxide
reduction. This is because adequate multi-electron re-
duction cannot be controlled, since it is not easy to hold
carbon dioxide on the surface of the metal catalyst on a
cathode. We try to generate a reaction on a site which
is suitable for multi-electron reduction by maintaining
and holding carbon dioxide with an adsorbed material
shown in Figure 7.
The following four conditions regarding the mate-
rial for a dark reaction need to be met to increase the
efficiency of multi-electron reduction on a cathode.
1) High adsorbed amount of carbon dioxide and
selectivity
2) Formation of the active point of catalyst (inside
and near pores)
3) High electric conductivity
4) High protonic conductivity
It is well known that a porous material is suitable
for carbon dioxide adsorption. We researched a porous
metal organic framework (MOF) or porous coordination

48 FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017)

 Y. Imanaka et al.: Artificial Photosynthesis Technology for Solving Environmental and Energy Issues
CO2 adsorption material
HO O CO2 + 2H+ + 2e– → HCOOH
CO2
OH
Adsorption
HO
O OH
Ligand
e–
H+
Electric
conductivity
Carbon
nanotube Proton
conductivity
Figure 7
Concept of development for cathode materials.
polymer (PCP), upon which very high expectations
have been placed recently. To add a catalytic active
point, there are two methods: one is to support fine
metal particles on the adsorbed material surface, and
the other is to make use of coordinated unsaturated
sites (open metal sites).
The M2(dobdc) using 2,5-Dihydroxyterephthalic
acid for ligand8) possesses open-site metal, which ad-
sorbs a large amount of carbon dioxide preferentially,
but expresses insulated properties. The electrons are
supplied from the electrode-side in our photosynthesis
system. For the reduction process in the pore of an ad-
sorption material, high electric conductivity is needed
inside of the material. Currently, we are trying to in-
crease the electric conductivity by combining a carbon
nanotube with MOF.
We confirmed that an effective way to achieve
high electric conductivity in hydrothermal synthesis is
to add to M2(dobdc) a carbon nanotube having a sur-
face that has been modified with a carboxyl group.
Research on proton conductivity is being done
with the development of a total system. Since the cath-
ode is immersed in an electrolyte in the current system,
protons can be moved easily. However, collecting the
dissolved reaction product is difficult. For this reason,
a system that does not use an electrolyte, a method
for forming a proton conductivity path in the pore of
MOF, and a non-aqueous system cell are also being
developed.
FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017)
5. Future perspective
In this paper, research on artificial photosyn-
thesis was introduced, focusing on material for use in
artificial photosynthesis. To apply this material to the
environmental and energy technology of an ICT so-
Catalytic ciety, it is imperative to develop a reaction unit at an
activity industrial level. We are trying to obtain high efficiency
for a total reaction unit by controlling electrons and
atoms in a material, controlling the nanostructure of a
film, and controlling micro- and macro-scale electrode
structures. We are researching key material for a high
Open
metal site performance, and we will study new material, structural
modification, and improvement of reaction property
and functionality by examining the simulation results
produced with a supercomputer.
6. Conclusion
Artificial photosynthesis is the ultimate tech-
nology for solving the issue of global warming and
depletion of fossil fuel resources. By using this tech-
nology, even in an emergency situation when a
power-supply grid cannot be used due to a natural di-
saster such as an earthquake, a secure society that can
maintain an energy source can be acquired.
Fujitsu will help to realize a sustainable society
using renewable energy by combining practical tech-
nologies and will develop basic technology for use in
the environmental and energy field.
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Yoshihiko Imanaka
Fujitsu Laboratories Ltd.
Dr. Imanaka is currently engaged in the
research of artificial photosynthesis and
energy creation technology.

Toshio Manabe
Fujitsu Laboratories Ltd.
Dr. Manabe is currently engaged in the
R&D on evaluation of artificial photosyn-
thesis system and dark reaction.

Toshihisa Anazawa
Fujitsu Laboratories Ltd.
Dr. Anazawa is currently engaged in
the R&D on material analysis, material
simulation, and artificial photosynthesis
system.

Hideyuki Amada
Fujitsu Laboratories Ltd.
Mr. Amada is currently engaged in the
R&D on light reaction of artificial photo-
synthesis systems.

50 FUJITSU Sci. Tech. J., Vol. 53, No. 2 (February 2017)